EP0025892B1 - Verfahren zur Hydroxylierung von Styrol und Styrolderivaten - Google Patents

Verfahren zur Hydroxylierung von Styrol und Styrolderivaten Download PDF

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Publication number
EP0025892B1
EP0025892B1 EP80105118A EP80105118A EP0025892B1 EP 0025892 B1 EP0025892 B1 EP 0025892B1 EP 80105118 A EP80105118 A EP 80105118A EP 80105118 A EP80105118 A EP 80105118A EP 0025892 B1 EP0025892 B1 EP 0025892B1
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EP
European Patent Office
Prior art keywords
formic acid
hydrogen peroxide
reaction
styrene
concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP80105118A
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German (de)
English (en)
French (fr)
Other versions
EP0025892A1 (de
Inventor
Gerhard Dr. Käbisch
Horst Malitius
Siegfried Raupach
Rudolf Trübe
Hans Wittmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Degussa GmbH
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Publication date
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Application filed by Degussa GmbH filed Critical Degussa GmbH
Priority to AT80105118T priority Critical patent/ATE4700T1/de
Publication of EP0025892A1 publication Critical patent/EP0025892A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/03—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by addition of hydroxy groups to unsaturated carbon-to-carbon bonds, e.g. with the aid of H2O2

Definitions

  • the invention relates to a process for the hydroxylation of styrene, its derivatives substituted in the aromatic nucleus or on the vinyl group by a methyl group or its derivatives substituted on the vinyl group by a hydroxymethyl group by reaction with formic acid at a concentration above 20% by weight and hydrogen peroxide at a concentration of less than 50 percent by weight and in an amount of less than 2 moles per mole of double bond to be hydroxylated.
  • “Hydroxylation” means that two hydroxyl groups are attached to the optionally substituted vinyl double bond, that is, a vicinal diol is formed.
  • cinnamon alcohol to phenylglycerol by reaction with formic acid at a concentration above 20% by weight and hydrogen peroxide at a concentration of less than 50% by weight in an amount of less than 2 moles per mole of double bond to be hydroxylated hydroxylate.
  • the formic acid is used in an amount of 18.2 moles per mole of double bond to be hydroxylated, and primarily a glycol monoformate is formed which then has to be saponified with a low yield.
  • the process according to the invention is now characterized in that the olefin to be hydroxylated is reacted at a temperature between 40 and 80 ° C. with less than 2 moles of formic acid per mole of double bond to be hydroxylated and the hydrogen peroxide, formic acid is used at a concentration between 20 and 100 percent by weight and keeps the concentration of hydrogen peroxide in the aqueous phase of the reaction mixture below 15 percent by weight for the entire duration of the reaction.
  • the reaction is preferably carried out at a temperature between 45 and 60 ° C.
  • the hydrogen peroxide is advantageously used in an amount of 1.1 to 1.5 moles per mole of double bond to be hydroxylated.
  • a hydrogen peroxide with a concentration of 15 to 40 percent by weight is preferably used.
  • the process according to the invention can be used, for example, to convert styrene into phenylglycol, the various vinyltoluenes into the corresponding tolylglycols, a-methylstyrene into a-methylphenylglycol or cinnamon alcohol into phenylglycerol.
  • the reactions surprisingly proceed very smoothly despite the relatively mild reaction conditions and lead to high yields of the desired vicinal diols within acceptable reaction times.
  • all of the formic acid to be used is preferably introduced.
  • the entire hydrogen peroxide to be used can also be presented.
  • the olefin to be hydroxylated is then slowly metered in.
  • the reaction mixture is stirred intensively. To improve the conversion, an appropriate post-reaction time is recommended after all the reactants have been combined in the reaction vessel.
  • the vicinal diols formed are usually present in solution in the aqueous phase.
  • aqueous solutions can go straight on be used.
  • the residual hydrogen peroxide content have a disruptive effect, but it is also desirable that the vicinal diols formed be isolated in a purer form. Then various measures can be considered for the processing.
  • the olefin used has not been completely reacted or polymerized to a small extent during the reaction, so that a second phase separates from the reaction mixture, a phase separation is carried out first.
  • the unreacted olefin can also be distilled off.
  • the decomposition can be caused by long standing at a higher temperature (digestion) or by the action of a suitable catalyst (e.g. transfer over a platinum fixed bed contact) or by a combination of these two measures.
  • reaction mixture is expediently thickened by distilling off water, if appropriate after neutralizing the formic acid present. If the formic acid contained has been neutralized, it is then extracted with a suitable solvent, for example ethyl acetate. The solvent is distilled off from the extract and the remaining crude diol residue is freed of any water still present, if appropriate by heating under reduced pressure. Alternatively, the formic acid contained in the reaction mixture can also be neutralized. It is then expedient either to carry out the thickening continuously in the manner of a steam distillation and to continue until the distillate contains only small amounts of formic acid.
  • a suitable solvent for example ethyl acetate.
  • the solvent is distilled off from the extract and the remaining crude diol residue is freed of any water still present, if appropriate by heating under reduced pressure.
  • the formic acid contained in the reaction mixture can also be neutralized. It is then expedient either to carry out the thickening continuously in the manner of a steam distillation and to continue until the distillate contains only small
  • the formic acid abortion is carried out discontinuously in such a way that after the main amount of formic acid has been removed, the residue is mixed with water again, thickened again and this operation repeated several times. The remaining residue of crude diol can then again be freed from volatile constituents which are still present by heating under reduced pressure.
  • the crude diols obtained in this way have purities of about 88 to 96%. If further purification is required, this can be effected in the usual way by recrystallization or by fractional distillation under reduced pressure.
  • styrene stabilized with 0.5 g of hydroquinone
  • the reaction mixture is first cooled and 8 g of styrene (and polystyrene) are removed by filtration. The turnover was therefore 96.2%.
  • the reaction mixture is then subjected to steam distillation at normal pressure until the formic acid concentration in the aqueous distillate has dropped from an initial 7.8% to 0.8%. The remaining portions of water and formic acid are removed by heating under reduced pressure. It leaves a residue of 271 g with a phenyl glycol content of 89.5%.
  • Example 2 is repeated with the difference that instead of a total of 312 g (3.0 mol) of styrene, now 354 (3.0 mol) of vinyl toluene (commercially available meta / para isomer mixture) are used.
  • reaction mixture After a further reaction time of a further 2 hours, 17 g of a-methylstyrene are distilled off from the reaction mixture. The turnover was therefore 95%.
  • the reaction mixture is neutralized with 285 g of sodium hydroxide solution (40%) and concentrated by topping 300 ml of water. A mixture remains that separates into two phases. The organic phase is separated off and washed in portions with the previously topped water.
  • wash waters are combined with the aqueous phase, catalytically freed of residual hydrogen peroxide and extracted five times in succession with 200 ml of ethyl acetate.
  • ethyl acetate extracts 70 g of diol with a purity of 96% are obtained.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
EP80105118A 1979-09-19 1980-08-28 Verfahren zur Hydroxylierung von Styrol und Styrolderivaten Expired EP0025892B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80105118T ATE4700T1 (de) 1979-09-19 1980-08-28 Verfahren zur hydroxylierung von styrol und styrolderivaten.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2937768A DE2937768C2 (de) 1979-09-19 1979-09-19 Verfahren zur Herstellung von Diolen bzw. Triolen durch Hydroxylierung von Styrol und Styrolderivaten
DE2937768 1979-09-19

Publications (2)

Publication Number Publication Date
EP0025892A1 EP0025892A1 (de) 1981-04-01
EP0025892B1 true EP0025892B1 (de) 1983-09-21

Family

ID=6081209

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80105118A Expired EP0025892B1 (de) 1979-09-19 1980-08-28 Verfahren zur Hydroxylierung von Styrol und Styrolderivaten

Country Status (10)

Country Link
US (1) US4308408A (ja)
EP (1) EP0025892B1 (ja)
JP (1) JPS5912645B2 (ja)
AR (1) AR226071A1 (ja)
AT (1) ATE4700T1 (ja)
AU (1) AU533937B2 (ja)
BR (1) BR8005947A (ja)
CA (1) CA1134867A (ja)
DE (1) DE2937768C2 (ja)
ES (1) ES493221A0 (ja)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NZ515366A (en) * 2001-11-08 2004-07-30 Univ Waikato Method for producing vicinal diols of compounds (especially lanosterol and cyclohexane derivatives) by reacting compounds with acids with pKa of less than or equal to 2 in the presence of one or more reagents capable of supplying hydroxy groups

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB634118A (en) * 1942-02-09 1950-03-15 Bataafsche Petroleum A process for the catalytic hydroxylation of olefinic compounds
US2555927A (en) * 1949-05-25 1951-06-05 Phillips Petroleum Co Hydroxylation of unsaturated compounds

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2794055A (en) * 1957-05-28 Catalytic hydrogenation of styrene
US2437648A (en) * 1943-09-15 1948-03-09 Research Corp Catalytic oxidation of unsaturated organic compounds
US2500599A (en) * 1944-12-19 1950-03-14 Shell Dev Catalytic hydroxylation of olefinic compounds
US2492201A (en) * 1946-06-07 1949-12-27 Swern Daniel Hydroxylation process
DE956505C (de) * 1953-01-18 1957-01-17 Ruhrchemie Ag Verfahren zur Herstellung von Tricyclo-(5, 2, 1, 0)-dekantriol-(3, 4, 8) bzw. -(3, 4, 9)
US2866826A (en) * 1953-05-14 1958-12-30 Heyden Newport Chemical Corp Method of making menthol from pinene
GB1078064A (en) * 1964-09-25 1967-08-02 Oril Soc Process for the manufacture of aliphatic aralkyl-ketones
US3337635A (en) * 1964-11-09 1967-08-22 Marathon Oil Co Method of producing ketols from hydrocarbons
GB1119612A (en) * 1966-04-20 1968-07-10 W J Bush & Company Ltd Hydroxylation of alkenyl substituted aromatic compounds

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB634118A (en) * 1942-02-09 1950-03-15 Bataafsche Petroleum A process for the catalytic hydroxylation of olefinic compounds
US2555927A (en) * 1949-05-25 1951-06-05 Phillips Petroleum Co Hydroxylation of unsaturated compounds

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
H.L. YALE et al. J. Am Chem Soc. 1950, 72, p. 3716-3718 *
Rodd's Chemistry of Carbon Compounds, 2nd Ed. Vol. III Part E S. 72, 73, 78 Kap. 1 "Aralkanediols, aralkanetriols" *

Also Published As

Publication number Publication date
BR8005947A (pt) 1981-03-31
DE2937768A1 (de) 1981-04-16
AU533937B2 (en) 1983-12-22
ES8104168A1 (es) 1981-04-16
ES493221A0 (es) 1981-04-16
JPS5912645B2 (ja) 1984-03-24
EP0025892A1 (de) 1981-04-01
JPS5651428A (en) 1981-05-09
AR226071A1 (es) 1982-05-31
AU6025080A (en) 1981-03-26
DE2937768C2 (de) 1985-03-21
ATE4700T1 (de) 1983-10-15
US4308408A (en) 1981-12-29
CA1134867A (en) 1982-11-02

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